US6274649B1 - Aqueous binding agent dispersion for cationic electro-dipcoat paint - Google Patents
Aqueous binding agent dispersion for cationic electro-dipcoat paint Download PDFInfo
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- US6274649B1 US6274649B1 US09/367,001 US36700199A US6274649B1 US 6274649 B1 US6274649 B1 US 6274649B1 US 36700199 A US36700199 A US 36700199A US 6274649 B1 US6274649 B1 US 6274649B1
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- 0 *([Y]Cc1ccccc1)[Y]Cc1ccccc1.*C.*C.C.C.CO.CO Chemical compound *([Y]Cc1ccccc1)[Y]Cc1ccccc1.*C.*C.C.C.CO.CO 0.000 description 1
- DTUGAVDVSCCQHL-UHFFFAOYSA-N C.C.[H]OCO Chemical compound C.C.[H]OCO DTUGAVDVSCCQHL-UHFFFAOYSA-N 0.000 description 1
- ABAMAZQNEYSUPW-UHFFFAOYSA-N C1=CC=CC=C1.CC.CC Chemical compound C1=CC=CC=C1.CC.CC ABAMAZQNEYSUPW-UHFFFAOYSA-N 0.000 description 1
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N CC(=O)CCO Chemical compound CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
Definitions
- the present invention relates to an aqueous binder dispersion for cationic electrodeposition coatings based on modified epoxy resins, and to a process for the preparation and use of the dispersion.
- Cationic electrodeposition coating is a common coating process, especially for priming, in which water-dilutable synthetic resins carrying cationic groups are applied to electroconductive elements with the aid of direct current.
- modified epoxy resins as binders for cationic electrodeposition coatings is known (U.S. Pat. Nos. 4,104,147; 4,260,720; 395,364; 4,268,542).
- the modified epoxy resins available hitherto for use in cationic electrodeposition coatings have only poor compatibility with aliphatic hydrocarbons, their elasticity is unsatisfactory, and they give films which cannot easily be overcoated and whose thickness should be further increased.
- EP 0 256 020 discloses water-dilutable binders for cationic electrodeposition coatings.
- a diepoxide compound if desired together with at least one monoepoxide compound, is converted to an epoxy resin in a polyaddition reaction carried out at from 100 to 195° C.
- the epoxy resin is subsequently modified by means of primary and/or secondary amines or salts thereof and/or the salt of a tertiary amine, a sulfide/acid or phosphine/acid mixture and, if desired, also with a polyfunctional alcohol, a polycarboxylic acid, a polysulfide or a polyphenol.
- solvents here must be added before or during addition of the amines. Accordingly, the high solvent content and low solids content are disadvantageous.
- the addition of solvents before/during addition of the amines means that excess solvent must be removed again after completion of the preparation of the binder dispersion.
- the object of the present invention is accordingly to develop novel binder dispersions based on modified epoxy resins which do not have the abovementioned disadvantages.
- the dispersions should have a low solvent content.
- the aim is to obviate the need for distillative removal of solvents after preparation of the dispersion.
- I a precursor which can be prepared, preferably at temperatures of from 120 to 180° C., particularly preferably from 125 to 150° C., from
- step B) subsequently or simultaneously reacting the secondary hydroxyl groups with epoxide groups of the epoxide/amine adduct prepared in step A) at temperatures of from 110 to 150° C., preferably at about 130° C., if desired with addition of a catalyst,
- novel binder dispersions can be obtained from readily accessible starting materials and are distinguished by good compatibility with aliphatic hydrocarbons and high elasticity.
- a high solids content is desirable for economic reasons. For a given reactor size, it allows a high solids yield per production batch to be achieved or, in other words, the production costs per kg of solids can be reduced at high solids contents.
- the solids content cannot be increased to an unlimited extent, since the dispersion must remain of sufficiently low viscosity for the subsequent processing steps, such as, for example, filtration.
- the upper limit is a flow viscosity of 25 seconds in a DIN 4 cup.
- High-viscosity resins can produce both low-viscosity and high-viscosity aqueous dispersions for a given solids content. This also applies to low-viscosity resins.
- the determining factors are of a complex nature and are generally not fully understood, even by the person skilled in the art. To this extent, the low viscosities of the novel binders with their relatively high solids contents were surprising.
- Component a in precursor I can be any compound containing two reactive epoxide groups and having an epoxide equivalent weight of below 1000, particularly preferably below 500.
- Particularly preferred epoxide compounds are polyphenol diglycidyl ethers prepared from polyphenols and epihalohydrins.
- polyphenols which can be employed are the following:
- bisphenol A and bisphenol F Particularly preferably: 1,1-bis(4-hydroxyphenyl)-n-heptane.
- 1,1-bis(4-hydroxyphenyl)-n-heptane Particularly preferably: 4,4-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butylphenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene and phenolic novolak resins are also suitable.
- Preferred epoxide compounds are diglycidyl ethers of polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol and bis(4-hydroxycyclohexyl)-2,2-propane.
- polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol and bis(4-hydroxycyclohexyl)-2,2-propane.
- diglycidyl esters of polycarboxylic acids such as, for example, oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimerized linolenic acid, etc.
- Typical examples are glycidyl adipate and glycidyl phthalate.
- hydantoin epoxides epoxidized polybutadiene and diepoxide compounds obtained by epoxidation of an olefinically unsaturated alicyclic compound.
- Component b of the precursor I can be an aromatic or aliphatic compound which contains a hydroxyl, carboxyl, phenol or thiol group, or a mixture of such compounds, and reacts in a monofunctional manner with respect to epoxide groups under the reaction conditions prevailing during the preparation of the novel modified epoxy resins.
- Component b is preferably a compound of the general formula R 1 —OH, where R 1 can have the following meaning:
- R 2 H, alkyl (preferably having 1 to 20 carbon atoms, particularly preferably t-butyl, nonyl or dodecyl),
- R 5 or a compound of the formula R 5 -SH, where R 5 can have the following meaning:
- R 5 alkyl (preferably having 1 to 20 carbon atoms, particularly preferably n-butyl or dodecyl), cycloalkyl (preferably cyclohexyl), aryl (particularly preferably phenyl) or aralkyl (particularly preferably benzyl),
- R 6 -OOC-CH 2 - or R 7 -OOC-CH 2 CH 2 -, where R 6 and R 7 alkyl having 1 to 8 carbon atoms, preferably butyl or 2-ethylhexyl,
- Component b is preferably a monophenol, diphenol, for example bisphenol A, or a mixture of mono- and diphenols.
- step I is preferably carried out at from 120 to 180° C., preferably at from 125 to 150° C.
- xylene or a propylene glycol monoalkyl ether such as propylene glycol methyl ether.
- the reaction of components a and b can be controlled in such a way that only phenolic hydroxyl groups, but not secondary hydroxyl groups, react with epoxide groups.
- the secondary hydroxyl groups are formed in the reaction of components a and b.
- the phosphine used can be any desired phosphine containing no interfering groups.
- phosphines are aliphatic, aromatic or alicyclic phosphines, specific examples of such phosphines which may be mentioned being the following: lower trialkylphosphines, such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributyl phosphine, mixed lower alkylphenylphosphines, such as phenyldimethylphosphine, phenyldiethylphosphine, phenyldipropylphosphine, diphenylmethylphosphine, di phenylethylphosphine, diphenylpropylphosphine, tri phenylphosphine, alicyclic phosphines, such as tetra methyleneethylphosphine and the like. Particular preference is given to triphenylphosphine.
- lower trialkylphosphines such as trimethylpho
- the selective conversion of the phenolic hydroxyl groups which can be controlled in a targeted matter by, in particular, the addition of the catalysts mentioned, has the result that the mean molecular weight of the precursor is below 1500 g/mol, preferably below 1000 g/mol. This reduction in the molecular weight reduces the viscosity and at the same time means that the precursor can be cooled sufficiently.
- the solids content of the precursor is ⁇ 90% by weight, preferably 95-100% by weight.
- step II primary, secondary or tertiary amines or their salts, or mixture of these compounds, can be added after or during reduction of the reaction temperature from step I.
- the temperatures are preferably from 60 to 130° C., preferably from 90 to 115° C.
- the amine should preferably be a water-soluble compound.
- examples of such amines are mono- and dialkylamines, such as methylamine, ethylamine, propyl amine, butylamine, dimethylamine, diethylamine, di propylamine, methylbutylamine and the like.
- alkanolamines such as, for example, methylethanolamine, diethanolamine and the like.
- dialkylaminoalkylamines such as, for example, dimethylaminoethylamine, diethylamino propylamine, dimethylaminopropylamine and the like.
- Polyamines containing primary and secondary amino groups can be reacted with the epoxides in the form of their ketimines.
- the ketimines are prepared from the polyamines in a known manner.
- the amines may also contain other groups, but these must not interfere with the reaction of the amine with the epoxide group nor result in gelling of the reaction mixture.
- the charges which are necessary for water-dilutability and electrodeposition can be generated by protonation by means of water-soluble acids (for example boric acid, formic acid, lactic acid, propionic acid, butyric acid, carbonic acid or preferably acetic acid) or alternatively by reaction of the oxirane groups with salts of an amine or a sulfide/acid or phosphine/acid mixture.
- water-soluble acids for example boric acid, formic acid, lactic acid, propionic acid, butyric acid, carbonic acid or preferably acetic acid
- the salt of an amine is preferably the salt of a tertiary amine.
- the amine component of the amine/acid salt is an amine which can be unsubstituted or substituted, such as in the case of hydroxylamine, where these substituents must not interfere with the reaction of the amine/acid salt and the reaction mixture must not gel.
- Preferred amines are tertiary amines, such as dimethyl ethanolamine, triethylamine, trimethylamine, tripropyl amine and the like. Examples of other suitable amines are given in U.S. Pat. No. 3,839,252 in column 5, line 3, to column 7, line 42.
- the amine/acid salt mixture is obtained in a known manner by reacting the amine with the acid.
- the addition of the amines increases the molecular weight to above 1000 g/mol, preferably to between 1500 and 2000 g/mol. This also results in an increase in the viscosity, which can be compensated again through the subsequent temperature increase.
- plasticizers and/or non-volatile diluents based on mono- or polyfunctional alcohols can, if desired, be added before or after addition of the amine.
- polypropylene glycol compounds such as Pluriol P 600, P 900, PE 3100 or Plastilit 3060 (all trademarks of BASF), can be used.
- the epoxide equivalent weight can be between 200 and 2000 g/mol, preferably between 400 and 700 g/mol, of component A).
- step B The epoxide groups remaining after step A) are reacted in step B), at elevated temperature, with secondary hydroxyl groups formed during the reaction of components a) and b).
- the reaction is preferably carried out at 110-150° C., particularly preferably at 130° C. If the temperature increase is not sufficient to reduce the viscosity, which likewise increases due to the increase in molecular weight, additional measures can be taken.
- step B) is preferably carried out in the presence of catalysts, particularly preferably in the presence of tertiary amino groups.
- catalysts particularly preferably in the presence of tertiary amino groups.
- separate addition is generally not necessary, since a catalyst of this type is introduced with the above-mentioned amines.
- the binders prepared in accordance with the invention are treated with crosslinking agents in step C).
- Suitable crosslinking agents are virtually all at least bifunctional compounds which react with hydroxyl groups, such as, for example polyalcohols, polyphenols, blocked polyisocyanates, phenolic resins and amino resins.
- the crosslinking agents are generally employed in an amount of from 5 to 50% by weight, preferably from 25 to 40% by weight, based on the binder, and at a temperature of ⁇ 150° C., preferably from 90 to 130° C.
- Suitable amino resin crosslinking agents are the hexamethyl ether of hexamethylolmelamine, the triethyl trimethyl ether of hexamethylolmelamine, the hexabutyl ether of hexamethylolmelamine, and the hexamethyl ether of hexamethylolmelamine and polymeric butylated melamine-formaldehyde resins. Alkylated urea-formaldehyde resins can also be used.
- the crosslinking agents used are preferably blocked polyisocyanates.
- any polyisocyanates can be used in which the isocyanate groups have been reacted with a compound in such a way that the blocked polyisocyanate formed is stable to hydroxyl groups at room temperature, but reacts therewith at elevated temperature, generally in the range from about 90 to about 300° C.
- the preparation of the blocked polyisocyanates can be carried out using any organic polyisocyanates which are suitable for the crosslinking. Preference is given to isocyanates containing from about 3 to about 36 carbon atoms, in particular from about 8 to about 15 carbon atoms.
- diisocyanates examples include trimethylene diisocyanate, tetramethylene diisocyanate, penta methylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,2-cyclohexylene di-isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 1-isocyanateomethyl-5-isocyanato-1,3,3-trimethyl
- polyisocyanates of higher isocyanate functionality examples thereof are tris(4-isocyanatophenyl)methane, 1,3,5-triisocyanato-benzene, 2,4,6-triisocyanatotoluene, 1,3,5-tris(6-isocyanatohexylbiuret), bis(2,5- diisocyanato-4-methyl-phenyl)methane, and polymeric polyisocyanates, such as dimers and trimers of diisocyanatotoluene. It is also possible to use mixtures of polyisocyanate.
- the organic polyisocyanates which are possible crosslinking agents in the invention may also be prepolymers derived, for example, from a polyol, including a polyether polyol or polyester polyol.
- the polyisocyanates can be blocked using any suitable aliphatic, cycloaliphatic or aromatic alkyl monoalcohols.
- suitable aliphatic alcohols such as methyl, ethyl, chloroethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, 3,3,5-trimethylhexyl, decyl and lauryl alcohol
- cycloaliphatic alcohols such as cyclopentanol and cyclohexanol
- aromatic alkyl alcohols such as phenylcarbinol and methylphenyl-carbinol.
- blocking agents are hydroxylamines, such as ethanolamine, oximes, such as methyl ethyl ketone oxime, acetone oxime and cyclohexanone oxime, or amines, such as dibutylamine and diisopropylamine.
- Said polyisocyanates and blocking agents can also be used in suitable mixing ratios for the preparation of the partially blocked polyisocyanates described above.
- polyfunctional alcohols or polycarboxylic acids can be added if desired. These preferably have a molecular weight of from 300 to 3500, in particular from 350 to 1000, and are preferably added in amounts of from 0 to 30% by weight, preferably from 2 to 10% by weight.
- the polyols which are suitable for the invention include diols, triols and higher polymeric polyols, such as polyester polyols and polyether polyols.
- R hydrogen or a lower alkyl radical
- examples are poly(oxytetramethylene) glycols and poly(oxyethylene) glycols.
- Further polyalkylene glycols which can be used in accordance with the invention are polyethylene glycols and polypropylene glycols, for example polypropylene glycol phenyl ether.
- the preferred polyalkylene ether polyols are poly(oxytetramethylene) glycols having a molecular weight in the range from 350 to 1000.
- Polyester polyols can likewise be used as polymeric polyol component in the invention.
- the polyester polyols can be obtained by polyesterfication of organic polycarboxylic acids or their anhydrides using organic polyols containing primary hydroxyl groups.
- the polycarboxylic acids and the polyols are aliphatic or aromatic dicarboxylic acids and diols.
- the diols used to prepare the polyesters include alkylene glycols, such as ethylene glycol, butylene glycol, propylene glycol, neopentyl glycol and other glycols, such as cyclohexanedimethanol.
- alkylene glycols such as ethylene glycol, butylene glycol, propylene glycol, neopentyl glycol and other glycols, such as cyclohexanedimethanol.
- the acid component of the polyester primarily consists of low-molecular-weight carboxylic acids or their anhydrides having 2 to 18 carbon atoms in the molecule.
- suitable acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid and glutaric acid.
- phthalic acid isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid and glutaric acid.
- polyester polyols derived from lactones are also possible. These products are obtained by reacting an ⁇ -caprolactone with a polyol. Such products are described in U.S. Pat. No. 3,169,945.
- the polylactone polyols obtained by this reaction are distinguished by the presence of a terminal hydroxyl group and by recurring polyester units derived from the lactone. These recurring moieties can conform to the formula.
- n is at least 4, preferably from 4 to 6, and the substituent is hydrogen, an alkyl radical, a cycloalkyl radical or an alkoxy radical.
- long-chain dicarboxylic acids are used.
- examples 10 thereof are dimeric fatty acids, such as, for example, dimeric linoleic acid.
- This component can advantageously be prepared, for example, in the following way.
- a high-molecular-weight diol for example a polyester diol, a polycaprolactone diol, a polyether diol, a poly carbonate diol or the like, is esterified using two moles of a hydroxyphenylcarboxylic acid or reacted with two moles of a hydroxyphenylcarboxylic ester.
- Suitable hydroxycarboxylic acids are p-hydroxybenzoic acid, p-hydroxyphenylacetic acid and 3-(4-hydroxyphenyl) propionic acid or their esters.
- hydroxyphenyl group is attached by transesterification, it is also possible to carry out a basic transesterification using the alkali metal phenoxide of the corresponding hydroxyphenylcarboxylic ester. After the end of the reaction, the product must be worked up under acidic conditions to give the desired polyphenol.
- any desired acidic polyesters can be reacted with p-hydroxyaniline to give the desired polyphenols.
- polyether diamines or similar polyamines are reacted with, for example, 4-hydroxy-3-methoxybenzaldehyde to give the polyphenols.
- step D a neutralization can be carried out in step D). This is preferably effected by addition of acids at from 90 to 110° C.
- step E) the mixture obtained in steps A) to D) is dispersed with addition of water.
- the particle size of the disperse phase is 30-1000 nm, preferably from 50 to 180 nm.
- coalescing solvents for example, coalescing solvents, pigments, surfactants, cross linking catalysts, antioxidants, fillers and antifoams
- additives for example, coalescing solvents, pigments, surfactants, cross linking catalysts, antioxidants, fillers and antifoams
- coalescing solvents for example, coalescing solvents, pigments, surfactants, cross linking catalysts, antioxidants, fillers and antifoams
- aqueous systems prepared with the aid of the binders according to the invention are particularly suitable for the cationic electrodeposition coating process; however, they can also be employed in conventional coating processes.
- coating substrates which can be used are optionally pre-treated metals, such as iron, steel, copper, zinc, brass, magnesium, tin, nickel, chromium and aluminum, but also impregnated paper and other electroconductive substrates.
- the binders according to the invention are also suitable for the preparation of pigment pastes, i.e. the binders can also be employed as grinding resin.
- the mixing ratios of the epoxy-containing organic material and of the organic tertiary amine which are reacted with one another are preferably selected in such a way that the base resin contains from 0.8 to 2.0 nitrogen atoms per molecule. Smaller amounts of quaternary nitrogen may result in poor wettability of the pigments, whereas higher amounts result in the resins becoming too water-soluble.
- Pigment pastes according to the invention are prepared by comminuting or dispersing a pigment in the grinding resin in a well-known manner.
- the pigment paste contains, as essential constituents, the grinding resin and at least one pigment.
- additives such as plasticizers, wetting agents, surfactants or antifoams, may also be present in the pigment composition.
- the pigments are generally ground in ball mills, sand mills, Cowles mills and continuous grinding units until the pigment has been comminuted to the desired particle size and has preferably be wetted by the resin or dispersed therein. After the comminution, the particle size of the pigment should be in the region of 10 ⁇ m or less. In general, comminution is continued to a Hegman fineness of from about 6 to 8.
- the grinding is preferably carried out in an aqueous dispersion of the grinding resin. The amount of water present in the mass to be ground should be sufficient to form a continuous aqueous phase.
- the pigment used in the invention can be the well-known pigments.
- titanium dioxide is the only or the principal white pigment.
- Other white pigments or extenders such antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate, barium carbonate, porcelain, clay, calcium carbonate, aluminum silicate, silicon dioxide, magnesium carbonate and magnesium silicate, can, however, also be used.
- colored pigments which can be used are cadmium yellow, cadmium red, carbon black, phthalocyanine blue, chromium yellow, toluidine red and hydrated iron oxide.
- the mixture is cooled to 65° C.
- the solids content is >97% (1 h at 130° C.).
- 1128 parts of a commercially available epoxy resin based bisphenol A having an epoxide equivalent weight (EEW) of 188, 262 parts of dodecylphenol, 31.4 parts of xylene and 228 parts of bisphenol A are introduced into a laboratory reactor heated by means of heat-exchange medium and fitted with stirrer, reflux condenser, thermometer and inert-gas inlet, and heated to 127° C. under nitrogen.
- 1.6 g of triphenylphosphine are added with stirring, whereupon an exothermic reaction commences and the temperature rises to 160° C.
- the mixture is cooled again to 130° C. and the epoxide content is then checked.
- the EEW of 532 indicates that >98% of the phenolic OH groups have reacted.
- 297.5 parts of Pluriol P 900 polypropylene glycol MW 900, BASF
- 105 parts of diethanolamine are added at 120° C. with further cooling.
- T max 127° C. the temperature has dropped to 110° C. (30 minutes)
- 51 parts of N,N-dimethylaminopropylamine are added.
- T max 140° C. the batch is allowed to react further at 130° C.
- Sedimentation stability no sediment after storage for 3 months at room temperature
- Viscosity 14 sec. (DIN 4 cup at 23° C.)
- Binder dispersion B is prepared by the method described in Example 2.1 from the starting materials listed below:
- Pluriol PE3100 propylene oxide-ethylene oxide polyether, BASF
- Sedimentation stability no sediment after storage for b 3 months at room temperature
- Binder dispersion C is prepared by the method described in Example 2.1 from the starting materials listed below:
- Plastilit 3060 (propylene glycol compound, BASF)
- Sedimentation stability no sediment after storage for 2 months at room temperature
- Viscosity 22 sec. (DIN 4 cup at 23° C.)
- a grinding resin is prepared in accordance with EP 505 445 B1, Example 1.3; for better handling, it is additionally neutralized and diluted with 2.82 parts of glacial acetic acid and 13.84 parts of demineralized water. The original solids content is thus reduced to
- a grinding resin containing blocked isocyanate groups and quaternary ammonium groups is prepared in accordance with DE-A 26 34 211, Example 2.
- the solids content of the resin is 87.6%.
- this resin is diluted to 60% with a 1:1 mixture of water and butyl glycol.
- Aqueous pigment pastes are prepared from the starting materials shown in the following table (Table 1) by the process described in EP 505 445 B1.
- Paste B describes the embodiment of a “lead-free” pigment paste.
- the electrodeposition baths are left to age for 3 days at room temperature with stirring.
- the films are deposited for 2 minutes at the applied voltage onto zinc-phosphated steel test panels connected as cathode without Cr(VI) rinsing in the pretreatment.
- the bath temperature is shown in Table 3.
- the deposited films are rinsed with deionized water and baked for 15 minutes at 175° C. (object temperature).
- dip coatings are listed in Table 3 along with their physical and electrical data and the properties of the 10 cured films resulting thereon.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE19703869 | 1997-02-03 | ||
DE19703869A DE19703869A1 (de) | 1997-02-03 | 1997-02-03 | Wäßrige Bindemitteldispersion für kationische Elektrotauchlacke |
PCT/EP1998/000493 WO1998033835A1 (de) | 1997-02-03 | 1998-01-30 | Wässrige bindemitteldispersion für kationische elektrotauchlacke |
Publications (1)
Publication Number | Publication Date |
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US6274649B1 true US6274649B1 (en) | 2001-08-14 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US09/367,001 Expired - Lifetime US6274649B1 (en) | 1997-02-03 | 1998-01-30 | Aqueous binding agent dispersion for cationic electro-dipcoat paint |
Country Status (8)
Country | Link |
---|---|
US (1) | US6274649B1 (ja) |
EP (1) | EP0961797B1 (ja) |
JP (1) | JP4149003B2 (ja) |
CN (1) | CN1246875A (ja) |
BR (1) | BR9807817A (ja) |
DE (2) | DE19703869A1 (ja) |
ES (1) | ES2196544T3 (ja) |
WO (1) | WO1998033835A1 (ja) |
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- 1998-01-30 EP EP98905370A patent/EP0961797B1/de not_active Expired - Lifetime
- 1998-01-30 US US09/367,001 patent/US6274649B1/en not_active Expired - Lifetime
- 1998-01-30 BR BR9807817-8A patent/BR9807817A/pt not_active IP Right Cessation
- 1998-01-30 DE DE59807866T patent/DE59807866D1/de not_active Expired - Lifetime
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GB2410719B (en) * | 2004-02-03 | 2006-03-01 | Easy Power Ltd | Improvements in lenses |
GB2410719A (en) * | 2004-02-03 | 2005-08-10 | Easy Power Ltd | Sealing lenses |
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US20110048948A1 (en) * | 2008-03-27 | 2011-03-03 | Basf Coatings Gmbh | Cathodic electrodeposition coatings containing polymethylene urea |
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US10081738B2 (en) | 2012-12-03 | 2018-09-25 | Basf Coatings Gmbh | Multicoat effect and/or color paint system and method for producing it, and its use |
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US11692105B2 (en) | 2017-10-09 | 2023-07-04 | Basf Coatings Gmbh | Electrocoats containing at least one triazine compound |
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US11186734B2 (en) | 2019-05-31 | 2021-11-30 | Axalta Coating Systems Ip Co., Llc | Epoxy resin emulsions for electrocoating |
WO2023078664A1 (en) | 2021-11-04 | 2023-05-11 | Basf Coatings Gmbh | Electrodeposition coating composition and its preparation |
WO2023078670A1 (en) | 2021-11-04 | 2023-05-11 | Basf Coatings Gmbh | Self-emulsifying blocked polyisocyanate dispersion and process for preparing the same |
Also Published As
Publication number | Publication date |
---|---|
CN1246875A (zh) | 2000-03-08 |
BR9807817A (pt) | 2000-03-08 |
EP0961797B1 (de) | 2003-04-09 |
EP0961797A1 (de) | 1999-12-08 |
JP4149003B2 (ja) | 2008-09-10 |
DE59807866D1 (de) | 2003-05-15 |
DE19703869A1 (de) | 1998-08-06 |
WO1998033835A1 (de) | 1998-08-06 |
JP2001509833A (ja) | 2001-07-24 |
ES2196544T3 (es) | 2003-12-16 |
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